JP7348804B2 - Dispersant compositions, coloring compositions and color filters - Google Patents

Description

The present invention relates to a dispersant composition, a colored composition containing the dispersant composition, and a color filter including a colored layer formed using the colored composition.

Conventionally, in the production of color filters used in liquid crystal displays and the like, known methods for applying colorants to substrates include pigment dispersion methods, dyeing methods, electrodeposition methods, printing methods, and inkjet methods. Among these, the pigment dispersion method is widely used from the viewpoint of spectral characteristics, durability, pattern shape, and accuracy. In the pigment dispersion method, for example, a coating film made of a colored composition mixed with a pigment, a dispersant, a dispersion medium (solvent), a binder resin, etc. is formed on a substrate, and radiation is irradiated through a photomask with a desired pattern shape. It is cured by irradiation, followed by alkaline development and post-baking.

For color filters, highly finely divided pigments are required to be dispersed in order to obtain high transmittance and high brightness. As such dispersants, Patent Document 1 and Patent Document 2 describe an A block having an amine value of 80 mgKOH/g or more and 150 mgKOH/g or less and having no amino group, and a B block having an amino group in its side chain. (See Patent Document 1 (paragraphs 0023 to 0039) and Patent Document 2 (paragraphs 0046 to 0067)).

Further, in order to obtain good color reproducibility and high contrast of color filters, increasing the concentration of the coloring material in the coloring composition is being considered. When increasing the pigment concentration, the proportion of the dispersant decreases relatively, so the dispersant is required to have high dispersibility (see, for example, Patent Document 3 (paragraph 0004)).

In alkaline development, an alkali-soluble binder resin plays a major role. However, in the case of a colored composition with a high concentration of pigment, the proportion of the binder resin, which is a developing component, decreases, resulting in a decrease in alkaline developability. Since the colored compositions using the dispersants of Patent Documents 1 and 2 do not have sufficient alkali developability, Patent Document 4 discloses a dispersant with a polylactone chain in the side chain as a dispersant that can impart excellent alkali developability. It has been proposed to use an AB block copolymer as a dispersant, which consists of an A block having a tertiary amino group and a B block having a tertiary amino group in its side chain (see Patent Document 4 (paragraphs 0023 to 0045)). .

JP2009-25813A JP 2017-182092 Publication Japanese Patent Application Publication No. 2009-265515 Japanese Patent Application Publication No. 2013-119568

However, the conventional dispersants used in the methods of Patent Documents 1 to 4 do not have sufficient dispersibility for colorants having aromatic rings. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dispersant composition that has excellent dispersibility of a coloring material having an aromatic ring.

The dispersant composition of the present invention, which has been able to solve the above problems, is a dispersant composition used in a coloring composition containing a colorant having an aromatic ring, and includes (a) a vinyl having an acidic group; A block copolymer having an A block containing a structural unit derived from a monomer and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), ( b) mixing at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound; and (c) a tertiary amine compound. The molar ratio ((b)/(c)) of the aromatic compound (b) to the tertiary amine compound (c) is 0.8 to 1.2.

〔式（１）において、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を示す。Ｒ¹⁴は水素原子またはメチル基を示す。Ｙ^-は対イオンを示す。〕

[In formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion. ]

〔式（２）において、Ｒ²¹およびＲ²²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²¹およびＲ²²が互いに結合して環状構造を形成していてもよい。Ｘ²は２価の連結基を示す。Ｒ²³は水素原子またはメチル基を示す。〕

[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ]

By using the dispersant composition of the present invention, a colored composition with high dispersibility of a coloring material having an aromatic ring and low viscosity can be obtained.

The dispersant composition of the present invention is a dispersant composition used for a coloring composition containing a coloring material having an aromatic ring, and includes (a) an A containing a structural unit derived from a vinyl monomer having an acidic group; block and a B block containing a structural unit represented by general formula (1) described later and a structural unit represented by general formula (2) described below; (b) aromatic dicarboxylic acid imide , at least one aromatic compound selected from the group consisting of an acidic group-containing aromatic compound and a phenolic hydroxy group-containing aromatic compound; (c) a tertiary amine compound; It is characterized in that the molar ratio ((b)/(c)) between the compound and the tertiary amine compound (c) is 0.8 to 1.2.

(a) Block copolymer The dispersant composition contains (a) a block copolymer. The block copolymer (a) may be used alone or in combinations of two or more. The block copolymer (a) has an A block containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (1) described below, and a structural unit represented by the general formula (2) described below. B block containing the structural unit.

In the present invention, "A block" can be translated as "A segment", and "B block" can be translated as "B segment". In the present invention, "vinyl monomer" refers to a monomer having a radically polymerizable carbon-carbon double bond in the molecule. The term "structural unit derived from a vinyl monomer" refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to become a carbon-carbon single bond. "(Meth)acrylic" refers to "at least one of acrylic and methacrylic." "(Meth)acrylate" refers to "at least one of acrylate and methacrylate." "(Meth)acryloyl" refers to "at least one of acryloyl and methacryloyl."

(A block)
The A block is a polymer block having a structural unit derived from a vinyl monomer having an acidic group. It is thought that the A block has an acidic group, which facilitates alkaline development. Therefore, the block copolymer can be suitably used in a coloring composition for a color filter used in the production of a color filter employing alkaline development.

Examples of the acidic group include a carboxy group (-COOH), a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-OPO ₃ H ₂ ), a phosphonic acid group (-PO ₃ H ₂ ), and a phosphinic acid group (- PO ₂ H ₂ ). The A block may have only one type of structural unit derived from a vinyl monomer having an acidic group, or may have two or more types of structural units.

The acidic group-containing vinyl monomer is preferably at least one selected from carboxy group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers, and phosphoric acid group-containing vinyl monomers. Among these, at least one selected from (meth)acrylic monomers having a carboxy group, (meth)acrylic monomers having a sulfonic acid group, and (meth)acrylic monomers having a phosphoric acid group is preferred.

Examples of vinyl monomers having a carboxy group include (meth)acrylic acid; hydroxy groups such as 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, and 2-(meth)acryloyloxyethyl phthalate; Examples include monomers obtained by reacting a vinyl monomer (preferably hydroxyalkyl (meth)acrylate) with an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride; crotonic acid; maleic acid; itaconic acid;

Examples of the vinyl monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, ethyl (meth)acrylate disulfonate, methylpropylsulfonic acid (meth)acrylamide, and ethyl (meth)acrylamide sulfonate.

Examples of the vinyl monomer having a phosphoric acid group include 2-(phosphonooxy)ethyl (meth)acrylate and the like.

The content of structural units derived from vinyl monomers having acidic groups is preferably 2% by mass or more in 100% by mass of A block, more preferably 5% by mass or more, still more preferably 7% by mass or more, and 20% by mass. % or less, more preferably 18% by mass or less, still more preferably 16% by mass or less. If the content of structural units derived from vinyl monomers having acidic groups is 2% by mass or more, the dissolution rate when neutralized with an alkali will be faster in alkaline development, and if it is 20% by mass or less, hydrophilicity will be high. Therefore, it is possible to prevent the formed pixels from becoming disorderly.

The A block may have a structural unit other than the structural unit derived from a vinyl monomer having an acidic group. Other structural units that may be included in the A block are not particularly limited as long as they are formed by a vinyl monomer that can be copolymerized with both a vinyl monomer having an acidic group and a vinyl monomer forming the B block described below. . Vinyl monomers that can form other structural units of the A block may be used alone, or two or more types may be used in combination.

Specific examples of vinyl monomers that can form other structural units of the A block include α-olefins, aromatic vinyl monomers, vinyl monomers containing heterocycles, vinylamides, vinyl carboxylates, dienes, and (meth)acrylic monomers. etc. These vinyl monomers may have a hydroxy group or an epoxy group.

Examples of the α-olefin include 1-hexene, 1-octene, and 1-decene.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene, and the like.
Examples of the vinyl monomer containing a heterocycle include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, and 4-vinylpyridine.
Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, 1-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.
Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate, and the like.
Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, and the like.

(Meth)acrylic monomers include (meth)acrylates having a chain alkyl group (straight chain alkyl group or branched alkyl group); (meth)acrylates having a cyclic alkyl group; (meth)acrylates having a polycyclic structure; Acrylate; (meth)acrylate having an aromatic ring group; (meth)acrylamide; (meth)acrylate having a polyalkylene glycol structural unit; (meth)acrylate having a hydroxy group; (meth)acrylate having a lactone-modified hydroxy group; alkoxy Examples include (meth)acrylates having a group; (meth)acrylates having a cyclic ether group; and the like.

The (meth)acrylate having a straight chain alkyl group is preferably a (meth)acrylate having a straight chain alkyl group in which the straight chain alkyl group has 1 to 20 carbon atoms; (Meth)acrylates having a straight chain alkyl group having 10 carbon atoms are more preferred, and (meth)acrylates having a straight chain alkyl group having 1 to 5 carbon atoms are more preferred. As the (meth)acrylate having a linear alkyl group, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, Examples include n-octyl (meth)acrylate, n-nonyl (meth)acrylate, decyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

The (meth)acrylate having a branched-chain alkyl group is preferably a (meth)acrylate having a branched-chain alkyl group in which the branched-chain alkyl group has 3 to 20 carbon atoms; Preferred are (meth)acrylates with a branched alkyl group of 10. Examples of the (meth)acrylate having a branched chain alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, 2- Examples include ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and the like.

The (meth)acrylate having a cyclic alkyl group is preferably a (meth)acrylate having a cyclic alkyl group having 6 to 12 carbon atoms. Examples of the cyclic alkyl group include a cyclic alkyl group having a monocyclic structure (for example, a cycloalkyl group). Specific examples of (meth)acrylates having a cyclic alkyl group with a monocyclic structure include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate.

The (meth)acrylate having a polycyclic structure is preferably a (meth)acrylate having a polycyclic structure having 6 to 12 carbon atoms. Examples of the polycyclic structure include cyclic alkyl groups having a bridged ring structure (eg, adamantyl group, norbornyl group, and isobornyl group). Specific examples of (meth)acrylates having a polycyclic structure include isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and 2-methyl-2-adamantyl. (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, and the like.

The (meth)acrylate having an aromatic group is preferably a (meth)acrylate having an aromatic group having 6 to 12 carbon atoms; Preferably, it is a (meth)acrylate having an aromatic group. Examples of the aromatic group include an aryl group, and may have a chain moiety such as an alkylaryl group, an aralkyl group, an aryloxyalkyl group, and the like. Specific examples of (meth)acrylates having an aromatic group include benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like.

Examples of (meth)acrylamide include (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, and the like.

Examples of (meth)acrylates having polyalkylene glycol structural units include polyethylene glycol (degree of polymerization = 2 to 10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth)acrylate, polyethylene glycol (Polymerization degree = 2 to 10) Propyl ether (meth)acrylate, polyethylene glycol (Polymerization degree = 2 to 10) (Meth)acrylate having a polyethylene glycol structural unit such as phenyl ether (meth)acrylate; Polypropylene glycol (Polymerization degree = 2-10) Methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2-10) Ethyl ether (meth)acrylate, polypropylene glycol (degree of polymerization = 2-10) Propyl ether (meth)acrylate, polypropylene glycol (degree of polymerization =2 to 10) Examples include (meth)acrylates having a polypropylene glycol structural unit such as phenyl ether (meth)acrylate.

Examples of (meth)acrylates having a hydroxy group include hydroxyalkyl such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples include (meth)acrylate.

Examples of the (meth)acrylate having a lactone-modified hydroxy group include those obtained by adding lactone to the above-mentioned (meth)acrylate having a hydroxy group, and those having caprolactone added are preferable. The amount of lactone added is preferably 1 mol to 10 mol, more preferably 1 mol to 5 mol. The (meth)acrylates having a lactone-modified hydroxy group include 1 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 2 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. 3 mol caprolactone adduct of 2-hydroxyethyl (meth)acrylate, caprolactone 4 mol adduct of 2-hydroxyethyl (meth)acrylate, caprolactone 5 mol adduct of 2-hydroxyethyl (meth)acrylate, caprolactone 10 mol adduct of 2-hydroxyethyl (meth)acrylate, etc. It will be done.

Examples of the (meth)acrylate having an alkoxy group include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and phenoxyethyl (meth)acrylate.

Examples of (meth)acrylates having a cyclic ether group include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, 2-(4-morpholinyl)ethyl (meth)acrylate, (3- Ethyloxetan-3-yl) methyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 2- Examples include [(2-tetrahydropyranyl)oxy]ethyl (meth)acrylate and 1,3-dioxane-(meth)acrylate.

The vinyl monomer that can form other structural units that can be included in the A block is preferably a (meth)acrylic monomer, such as (meth)acrylate having a chain alkyl group, (meth)acrylate having an aromatic ring group, or polyalkylene glycol. At least one member selected from the group consisting of (meth)acrylates having structural units, (meth)acrylates having hydroxy groups, (meth)acrylates having lactone-modified hydroxy groups, and (meth)acrylates having cyclic ether groups. It is more preferable. The vinyl monomers that can be used in the A block can be used alone or in combination of two or more.

The A block is at least one vinyl monomer selected from the group consisting of (meth)acrylates having a chain alkyl group, (meth)acrylates having a cyclic alkyl group, and (meth)acrylates having an aromatic ring group. When having structural units derived from the A block, the total content of these structural units is preferably 8% by mass or more in 100% by mass of A block, more preferably 10% by mass or more, still more preferably 13% by mass or more, The content is preferably 98% by mass or less, more preferably 95% by mass or less, even more preferably 70% by mass or less, even more preferably 62% by mass or less, even more preferably 54% by mass or less.

The A block is (meth)acrylamide, (meth)acrylate having a polyalkylene glycol structural unit, (meth)acrylate having a hydroxy group, (meth)acrylate having a lactone-modified hydroxy group, (meth)acrylate having an alkoxy group, And, when it has a structural unit derived from at least one vinyl monomer selected from the group consisting of (meth)acrylate having a cyclic ether group, the total content of these structural units in 100% by mass of A block is The content is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 90% by mass or less. , more preferably 85% by mass or less, still more preferably 80% by mass or less.

The A block preferably contains a structural unit represented by the general formula (9), that is, a structural unit derived from the (meth)acrylate having the lactone-modified hydroxy group. Since the structural unit represented by general formula (9) has an ester bond moiety and a terminal hydroxyl group in the side chain, it has high affinity with the dispersion medium and binder resin, and improves the alkaline developability of the colored composition. enhance

〔一般式（９）において、ｎ９は１～１０の整数を表す。Ｒ⁹¹は炭素数が１～１０のアルキレン基を表す。Ｒ⁹²は炭素数が１～１０のアルキレン基を表す。Ｒ⁹³は水素原子またはメチル基を表す。〕

[In general formula (9), n9 represents an integer of 1 to 10. R ⁹¹ represents an alkylene group having 1 to 10 carbon atoms. R ⁹² represents an alkylene group having 1 to 10 carbon atoms. R ⁹³ represents a hydrogen atom or a methyl group. ]

In the formula (9), n9 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5.

The alkylene group having 1 to 10 carbon atoms represented by R ⁹¹ may be linear or branched, but linear is preferable. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ⁹¹ include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, Examples include nonamethylene group and decamethylene group. R ⁹¹ is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 3 to 8 carbon atoms.

The alkylene group having 1 to 10 carbon atoms represented by R ⁹² may be linear or branched, but linear is preferable. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ⁹² include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, Examples include nonamethylene group, decamethylene group, and 1-methylethylene group. R ⁹² is preferably an alkylene group having 1 to 5 carbon atoms.

When the A block contains a structural unit represented by general formula (9), its content is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably is 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 95% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less. By setting the content of the structural unit derived from the (meth)acrylate having a lactone-modified hydroxy group within the above range, the alkali developability of the block copolymer can be improved.

Moreover, it is preferable that the A block does not have an amino group. That is, it is preferable that the vinyl monomer constituting the A block does not contain a vinyl monomer having an amino group. If a large amount of amino groups are present in the A block, when used as a dispersant for a colorant, the colorant will be adsorbed to both the A block and the B block, reducing the dispersion performance of the colorant. The content of the structural unit derived from the vinyl monomer having an amino group in the A block is preferably 2% by mass or less, more preferably 1% by mass or less, even more preferably 0.1% by mass or less, and most preferably 0% by mass. %.

When two or more types of structural units are contained in the A block, the various structural units contained in the A block may be contained in any form such as random copolymerization or block copolymerization in the A block. , is preferably contained in a random copolymerized form from the viewpoint of uniformity. For example, the A block may be formed of a copolymer of a structural unit consisting of an a1 block and a structural unit consisting of an a2 block.

(B block)
The B block is a polymer block having a structural unit represented by general formula (1) and a structural unit represented by general formula (2). Since the B block has a quaternary ammonium base in addition to a tertiary amino group, it is considered to have a high affinity with the coloring material.

(Structural unit represented by general formula (1))
The structural unit represented by general formula (1) has a quaternary ammonium salt in its structure. The number of structural units represented by general formula (1) in the B block may be one type or two or more types.

〔式（１）において、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を示す。Ｒ¹⁴は水素原子またはメチル基を示す。Ｙ^-は対イオンを示す。〕

[In formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion. ]

Examples of the chain hydrocarbon group represented by R ¹¹ to R ¹³ include a linear alkyl group, a branched alkyl group, and the like. The number of carbon atoms in the linear alkyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, etc. can be mentioned. The number of carbon atoms in the branched alkyl group is preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group, isooctyl group, and the like.

Examples of the substituents possessed by the chain hydrocarbon groups represented by R ¹¹ to R ¹³ include halogen groups, alkoxy groups, benzoyl groups (-COC ₆ H ₅ ), and hydroxy groups.

Examples of the cyclic hydrocarbon group represented by R ¹¹ to R ¹³ include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain moiety. The number of carbon atoms in the cyclic alkyl group is preferably 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The number of carbon atoms in the aromatic group is preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Examples of the aromatic group include a phenyl group, tolyl group, xylyl group, mesityl group, and the like. Examples of the cyclic alkyl group having a chain moiety and the chain moiety of an aromatic group having a chain moiety include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. Examples include 1 to 3 alkylene groups.

Examples of the substituent on the cyclic hydrocarbon group represented by R ¹¹ to R ¹³ include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxy group.

Examples of the cyclic structure formed by two or more of R ¹¹ to R ¹³ bonded to each other include a 5- to 7-membered nitrogen-containing heteromonocyclic ring or a condensed ring formed by condensing two of these. . The nitrogen-containing heterocycle preferably has no aromaticity, and is more preferably a saturated ring. Specific examples include structures represented by the following formulas (1-1), (1-2), and (1-3).

〔一般式（１－１）、（１－２）、（１－３）において、Ｒ¹⁵は、Ｒ¹¹～Ｒ¹³のいずれかである。Ｒ¹⁶は、炭素数１～６のアルキル基を示す。ｌは０～５の整数を表す。ｍは０～４の整数を表す。ｎは０～４の整数を表す。＊は結合手を表す。ｌが２～５、ｍが２～４、ｎが２～４の場合、複数存在するＲ¹⁶は、それぞれ同一でも異なっていてもよい。〕

[In general formulas (1-1), (1-2), and (1-3), R ¹⁵ is any one of R ¹¹ to R ¹³ . R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. * represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ^16s may be the same or different. ]

In general formula (1), the divalent linking group X ¹ is, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH-R ¹⁷ - group (amide group), a -COO-R ¹⁸ - group (ester group), preferably a -CONH-R ¹⁷ - group and/or a -COO-R ¹⁸ - group, more preferably a -COO-R ¹⁸ - group. Note that the bonding direction of the amide group and the ester group is not particularly limited, but the bonding mode of the amide group is preferably C-CO-NH-R ¹⁷ -N ⁺ R ¹¹ R ¹² R ¹³ , and the bonding mode of the ester group is C—CO—O—R ¹⁸ —N ⁺ R ¹¹ R ¹² R ¹³ is preferred.

The R ¹⁷ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms. is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and the like.

The R ¹⁸ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and the like.

Examples of Y ^- include halogen anions, carboxylate anions, nitroxide anions, sulfate anions, sulfonate anions, and phosphate anions.

Examples of the halogen anion include a fluoro anion, a chloro anion, a bromo anion, and an iodo anion.
Examples of the carboxylate anions include alkyl carboxylate anions such as acetate anions and propionate anions; aromatic carboxylate anions such as benzoate anions.
Examples of the sulfate anions include alkyl sulfate anions such as methyl sulfate anions and ethyl sulfate anions; aromatic sulfate anions such as phenyl sulfate anions and benzyl sulfate anions.
Examples of the sulfonate anions include alkylsulfonate anions such as methanesulfonate anion and ethanesulfonate anion; aromatic sulfonate anions such as benzenesulfonate anion and toluenesulfonate anion.
Examples of the phosphate anion include alkyl phosphate anions such as methyl phosphate anion; aromatic phosphate anions such as phenyl phosphate anion.

Specific examples of vinyl monomers forming the structural unit represented by formula (1) include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxypropyltrimethylammonium chloride, and (meth)acryloyloxybutyltrimethylammonium chloride. , (meth)acryloyloxyethylbenzyldimethylammonium chloride, (meth)acryloyloxypropylbenzyldimethylammonium chloride, (meth)acryloyloxybutylbenzyldimethylammonium chloride, (meth)acryloyloxyethylbenzyldiethylammonium chloride, (meth)acryloyloxy Propylbenzyldiethylammonium chloride, (meth)acryloyloxybutylbenzyldiethylammonium chloride, (meth)acryloylamide propylbenzyldimethylammonium chloride, (meth)acryloyloxyethyltrimethylammonium bromide, (meth)acryloyloxypropyltrimethylammonium bromide, (meth) ) Acryloyloxybutyltrimethylammonium bromide, (meth)acryloyloxyethylbenzyldimethylammonium bromide, (meth)acryloyloxypropylbenzyldimethylammonium bromide, (meth)acryloyloxybutylbenzyldimethylammonium bromide, (meth)acryloyloxyethylbenzyldiethylammonium Bromide, (meth)acryloyloxypropylbenzyldiethylammonium bromide, (meth)acryloyloxybutylbenzyldiethylammonium bromide, (meth)acryloylamidepropylbenzyldimethylammonium bromide, (meth)acryloyloxyethyltrimethylammonium iodide, (meth)acryloyl Oxypropyltrimethylammonium iodide, (meth)acryloyloxybutyltrimethylammonium iodide, (meth)acryloyloxyethylbenzyldimethylammonium iodide, (meth)acryloyloxypropylbenzyldimethylammonium iodide, (meth)acryloyloxybutylbenzyldimethyl Ammonium iodide, (meth)acryloyloxyethylbenzyldiethylammonium iodide, (meth)acryloyloxypropylbenzyldiethylammonium iodide, (meth)acryloyloxybutylbenzyldiethylammonium iodide, (meth)acryloyloxyethyltrimethylammonium fluoride , (meth)acryloyloxypropyltrimethylammonium fluoride, (meth)acryloyloxybutyltrimethylammonium fluoride, (meth)acryloyloxyethylbenzyldimethylammonium fluoride, (meth)acryloyloxypropylbenzyldimethylammonium fluoride, (meth) Acryloyloxybutylbenzyldimethylammonium fluoride, (meth)acryloyloxyethylbenzyldiethylammonium fluoride, (meth)acryloyloxypropylbenzyldiethylammonium fluoride, (meth)acryloyloxybutylbenzyldiethylammonium fluoride, (meth)acryloyloxy Ethyltrimethylammonium = methylsulfate, (meth)acryloyloxypropyltrimethylammonium = methylsulfate, (meth)acryloyloxybutyltrimethylammonium = methylsulfate, (meth)acryloyloxyethyldimethylethylammonium = ethylsulfate, (meth) ) Acryloyloxypropyl dimethylethylammonium = ethyl sulfate, (meth)acryloyloxybutyldimethylethylammonium = ethyl sulfate, (meth)acryloyloxyethyltrimethylammonium = toluene-4-sulfonate, (meth)acryloyloxypropyltrimethylammonium = Toluene-4-sulfonate, (meth)acryloyloxybutyltrimethylammonium = toluene-4-sulfonate, (meth)acryloylamidepropyltrimethylammonium = methylsulfate, (meth)acryloylamidepropylethyldimethylammonium = ethylsulfate, etc. It will be done.

The content of the structural unit represented by general formula (1) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and 85% by mass in 100% by mass of the B block. % or less, more preferably 80% by mass or less, further preferably 75% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less. It is considered that by setting the content of the structural unit represented by the general formula (1) within this range, it has a high affinity with the coloring material.

(Structural unit represented by general formula (2))
The structural unit represented by general formula (2) has a tertiary amine structure. The number of structural units represented by general formula (2) in the B block may be one type or two or more types.

〔式（２）において、Ｒ²¹およびＲ²²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²¹およびＲ²²が互いに結合して環状構造を形成していてもよい。Ｘ²は２価の連結基を示す。Ｒ²³は水素原子またはメチル基を示す。〕

[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ]

Examples of the chain hydrocarbon group represented by R ²¹ and R ²² include a linear alkyl group and a branched alkyl group. The number of carbon atoms in the linear alkyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, etc. can be mentioned. The number of carbon atoms in the branched alkyl group is preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, neopentyl group, isooctyl group, and the like.

Examples of the substituent on the chain hydrocarbon group represented by R ²¹ and R ²² include a halogen group, an alkoxy group, a benzoyl group (-COC ₆ H ₅ ), and a hydroxy group.

Examples of the cyclic hydrocarbon group represented by R ²¹ and R ²² include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain moiety. The number of carbon atoms in the cyclic alkyl group is preferably 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The number of carbon atoms in the aromatic group is preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Examples of the aromatic group include a phenyl group, tolyl group, xylyl group, mesityl group, and the like. Examples of the cyclic alkyl group having a chain moiety and the chain moiety of an aromatic group having a chain moiety include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. Examples include 1 to 3 alkylene groups.

Examples of the substituent of the cyclic hydrocarbon group represented by R ²¹ and R ²² include a halogen group, an alkoxy group, a chain alkyl group, and a hydroxy group.

The cyclic structure formed by bonding R ²¹ or R ²² to each other includes, for example, a 5- to 7-membered nitrogen-containing monocyclic ring or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, and is more preferably a saturated ring. Specific examples include structures represented by the following formulas (2-1), (2-2), and (2-3).

〔一般式（２－１）、（２－２）、（２－３）において、Ｒ²⁴は、炭素数１～６のアルキル基を示す。ｌは０～５の整数を表す。ｍは０～４の整数を表す。ｎは０～４の整数を表す。＊は結合手を表す。ｌが２～５、ｍが２～４、ｎが２～４の場合、複数存在するＲ²⁴は、それぞれ同一でも異なっていてもよい。〕

[In general formulas (2-1), (2-2), and (2-3), R ²⁴ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. * represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ^24s may be the same or different. ]

In the above general formula (2), the divalent linking group X ² is, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH-R ²⁵ - group (amide group), -COO-R ²⁶ - groups (ester groups), etc., preferably -COO-R ²⁶ - group and/or -CONH-R ²⁵ - group, preferably -CONH-R ²⁵ - group and/or -COO-R ²⁶ - group, more preferably -COO-R ²⁶ - group. Note that the bonding direction of the amide group and the ester group is not particularly limited, but the bonding mode of the amide group is preferably C-CO-NH-R ²⁵ -NR ²¹ R ²² , and the bonding mode of the ester group is C-CO -OR ²⁶ -NR ²¹ R ²² is preferred.

The R ²⁵ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and the like.

The R ²⁶ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and the like.

The content of the structural unit represented by the general formula (2) is preferably 15% by mass or more in 100% by mass of B block, more preferably 20% by mass or more, still more preferably 25% by mass or more, even more preferably 40% by mass or more. The content is at least 50% by mass, more preferably at least 50% by mass, preferably at most 90% by mass, more preferably at most 80% by mass, even more preferably at most 70% by mass. It is considered that by setting the content of the structural unit represented by the general formula (2) within this range, it has a high affinity with the coloring material.

The B block may include only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may contain other structural units. From the viewpoint of maintaining affinity with the coloring material, the total content of the structural unit represented by general formula (1) and the structural unit represented by general formula (2) in the B block is 80% by mass or more. is preferable, more preferably 90% by mass or more, still more preferably 95% by mass or more. Moreover, it is preferable that the B block does not substantially contain a structural unit derived from a vinyl monomer having an acidic group. That is, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 5% by mass or less, more preferably 3% by mass or less in 100% by mass of the B block.

Specific examples of vinyl monomers that can form other structural units of block B include the same ones as those exemplified as specific examples of vinyl monomers that can form other structural units of block A.

When two or more types of structural units are contained in the B block, the various structural units contained in the B block may be contained in any form such as random copolymerization or block copolymerization in the B block. , is preferably contained in a random copolymerized form from the viewpoint of uniformity. For example, the B block may be formed of a copolymer of a structural unit consisting of a b1 block and a structural unit consisting of a b2 block.

(Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. In addition, the linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is A and the B block is B. When expressed as, (A-B) _m type, (A-B) _m -A type, (B-A) _m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3). A copolymer having at least one type of structure selected from the following is preferable. Among these, a diblock copolymer represented by AB is preferred from the viewpoint of handling properties during processing and physical properties of the composition. By constituting a diblock copolymer represented by AB, a structural unit derived from a vinyl monomer having an acidic group in the A block and a vinyl monomer having a tertiary amino group in the B block. It is thought that the structural unit and the structural unit derived from the vinyl monomer having a quaternary ammonium base are localized and can efficiently interact favorably with the colorant, solvent, and binder resin.

The content of the A block is preferably 35% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and preferably 85% by mass or less, based on 100% by mass of the entire block copolymer. It is more preferably 80% by mass or less, and still more preferably 75% by mass or less. The content of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and preferably 65% by mass or less, based on 100% by mass of the entire block copolymer. The content is more preferably 60% by mass or less, further preferably 55% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less. By adjusting the content of A block and B block within the above range, heat resistance and dispersion performance when used as a dispersant can be achieved in a well-balanced manner.

The mass ratio of A block to B block (A block/B block) in the block copolymer is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, and 95 /5 or less is preferable, more preferably 90/10 or less, still more preferably 80/20 or less. If the mass ratio of the A block to the B block is within the above range, it is possible to achieve both dispersion performance and alkaline developability when used as a dispersant in a well-balanced manner.

The content of structural units derived from vinyl monomers having acidic groups in the block copolymer (a) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, The content is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less.

The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the block copolymer (a) is preferably 5% by mass or more, more preferably The content is 10% by mass or more, more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less.

The molecular weight of the block copolymer (a) is measured by gel permeation photography (hereinafter referred to as "GPC"). The weight average molecular weight (Mw) of the block copolymer (a) is preferably 5,000 or more, more preferably 7,000 or more, even more preferably 9,000 or more, and preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000. It is as follows. If the weight average molecular weight is within the above range, the dispersion performance will be better when used as a dispersant.

The molecular weight distribution (PDI) of the block copolymer (a) is preferably 3.0 or less, more preferably 2.0 or less, and even more preferably 1.6 or less. In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of block copolymer)/(number average molecular weight (Mn) of block copolymer). The smaller the PDI, the narrower the width of the molecular weight distribution, resulting in a copolymer with uniform molecular weight, and when the value is 1.0, the width of the molecular weight distribution is the narrowest. That is, the lower limit value of PDI is 1.0. If the molecular weight distribution (PDI) of the block copolymer exceeds 3.0, it will include those with small molecular weights and those with large molecular weights.

(Method for producing block copolymer)
The method for producing the block copolymer includes a method in which the A block is first produced by a polymerization reaction of vinyl monomers, and the monomer of the B block is polymerized onto the A block; A method of polymerizing block monomers; A method of manufacturing the A block and B block separately and then coupling the A block and B block; a method of manufacturing the A block first and adding the formula (2) to the B block. A monomer composition containing a vinyl monomer that can form a structural unit is polymerized, and the tertiary amine structure of a part of the structural unit represented by formula (2) in the obtained polymer is quaternized. Method: A monomer composition containing a vinyl monomer capable of forming a structural unit represented by formula (2) is polymerized, a monomer of A block is polymerized to this polymer, and the formula (2) in the obtained polymer is polymerized. ) A method for quaternizing the tertiary amine structure of a part of the structural unit represented by formula (2); A block and a block having the structural unit represented by formula (2) are separately manufactured, and these blocks are cupped. Examples include a method of quaternizing some tertiary amine structures of the structural units represented by formula (2) in the obtained polymer after ringing.

The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the block copolymer is preferably one polymerized by living radical polymerization. Living radical polymerization maintains the simplicity and versatility of conventional radical polymerization, while being less likely to cause termination reactions or chain transfer, and allows for growth without being hindered by side reactions that deactivate growing terminals, resulting in improved molecular weight distribution. This is preferable because it is easy to precisely control and produce a polymer with a uniform composition.

Depending on the method of stabilizing the polymer growth terminal, living radical polymerization methods include a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); and a method using an organic tellurium compound. There are methods such as the method used (TERP method). Among these methods, it is preferable to use the TERP method from the viewpoint of diversity of monomers that can be used, control of molecular weight in the polymer region, uniform composition, or coloring.

The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator. For example, WO 2004/14848, WO 2004/14962, WO This is the method described in No. 2004/072126 and International Publication No. 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(a) A vinyl monomer is polymerized using an organic tellurium compound represented by general formula (11).
(b) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (11) and an azo polymerization initiator.
(c) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (11) and an organic ditelluride compound represented by general formula (12).
(d) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (11), an azo polymerization initiator, and an organic ditelluride compound represented by general formula (12).

［一般式（１１）において、Ｒ¹は、炭素数１～８のアルキル基、アリール基または芳香族ヘテロ環基を示す。Ｒ²およびＲ³は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示す。Ｒ⁴は、炭素数１～８のアルキル基、アリール基、置換アリール基、芳香族ヘテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基を示す。
一般式（１１）において、Ｒ¹は、炭素数１～８のアルキル基、アリール基または芳香族ヘテロ環基を示す。］

[In the general formula (11), R ¹ represents an alkyl group, an aryl group, or an aromatic heterocyclic group having 1 to 8 carbon atoms. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group.
In the general formula (11), R ¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group. ]

Specifically, the organic tellurium compound represented by the general formula (11) is ethyl-2-methyl-2-methyltellanyl-propionate, ethyl-2-methyl-2-n-butyltellanyl-propionate, (2-hydroxyethyl) -2-methyl-2-methyltellanyl-propionate, etc., organic tellurium described in WO 2004/14848, WO 2004/14962, WO 2004/072126, and WO 2004/096870 Examples include compounds. Specific examples of the organic ditelluride compound represented by the general formula (12) include dimethyl ditelluride, diethyl ditelluride, and the like. The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization. For example, 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1'-azobis(1-cyclohexanecarbonitrile) (ACHN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70), and the like.

In the polymerization step, in a container purged with an inert gas, the vinyl monomer and the organic tellurium compound of general formula (11) are added, depending on the type of vinyl monomer, for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc. An azo polymerization initiator and/or an organic ditelluride compound of general formula (12) are mixed. At this time, examples of the inert gas include nitrogen, argon, helium, and the like. Preferably, argon or nitrogen is used. The amount of the vinyl monomer used in (a), (b), (c) and (d) may be adjusted as appropriate depending on the physical properties of the desired copolymer.

The polymerization reaction can be carried out without a solvent, but it may also be carried out using an aprotic or protic solvent commonly used in radical polymerization and stirring the mixture. Examples of aprotic solvents that can be used include anisole, benzene, toluene, propylene glycol monomethyl ether acetate, tetrahydrofuran (THF), and ethyl acetate. Further, examples of the protic solvent include water, methanol, ethanol, isopropanol, and 1-methoxy-2-propanol. The solvents may be used alone or in combination of two or more. The amount of solvent to be used may be adjusted as appropriate, and is preferably 0.01 ml to 50 ml per 1 g of vinyl monomer. Although the reaction temperature and reaction time may be adjusted as appropriate depending on the molecular weight or molecular weight distribution of the resulting copolymer, stirring is usually carried out at 0° C. to 150° C. for 1 minute to 100 hours. After the polymerization reaction is completed, the desired copolymer can be separated from the resulting reaction mixture by removing the solvent used, residual vinyl monomer, etc., by ordinary separation and purification means.

The growing end of the copolymer obtained by the polymerization reaction is in the form of -TeR ¹ (in the formula, R ¹ is the same as above) derived from a tellurium compound, and is deactivated by operation in air after the polymerization reaction is completed. However, tellurium atoms may remain. Since a copolymer with tellurium atoms remaining at the terminals is colored and has poor thermal stability, it is preferable to remove the tellurium atoms. Methods for removing tellurium atoms include a radical reduction method; a method of adsorption with activated carbon, etc.; a method of adsorbing metal with an ion exchange resin, etc.; and a combination of these methods can also be used. The other end of the copolymer obtained by the polymerization reaction (the end opposite to the growing end) is -CR ² R ³ R ⁴ derived from a tellurium compound (wherein R ² , R ³ and R ⁴ are of the formula The form is the same as R ² , R ³ and R ⁴ in (11).

When quaternizing the tertiary amine group of the structural unit represented by formula (2), examples of quaternizing agents include alkyl halides such as methyl chloride; aralkyl halides such as benzyl chloride; sulfuric acids such as diphenyl sulfate. Examples include diaryl; dialkyl sulfate such as dimethyl sulfate; and alkyl aromatic sulfonate such as methyl p-toluenesulfonate. A method for quaternizing the tertiary amine structure of a part of the structural unit represented by formula (2) in the polymer includes a method of bringing the polymer into contact with a quaternizing agent. Specifically, a method may be mentioned in which a monomer composition containing a vinyl monomer capable of forming a structural unit represented by formula (2) is polymerized, and then a quaternizing agent is added to this reaction solution and stirred. . The temperature of the reaction solution to which the quaternizing agent is added is preferably 25°C to 65°C, more preferably 55°C to 65°C, and the stirring time is preferably 1 hour to 40 hours, more preferably 5 hours to 20 hours. It is.

(b) Aromatic compound The dispersant composition of the present invention comprises (b) at least one compound selected from the group consisting of an aromatic dicarboxylic acid imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound. Contains aromatic compounds. When the dispersant composition contains the aromatic compound (b), the dispersibility becomes good. (b) Only one type of aromatic compound may be blended, or two or more types may be used in combination.

Aromatic dicarboxylic acid imide has an aromatic ring and an imide group (-C(=O)NHC(=O)-) directly bonded to the aromatic ring in its molecule. Both ends of the imide group may be bonded to one aromatic ring or may be bonded to different aromatic rings, but preferably both ends are bonded to one aromatic ring. As the aromatic dicarboxylic acid imide, a compound represented by general formula (3) is preferable.

〔一般式（３）において、環Ａは置換基を有していてもよい芳香環を表す。〕

[In general formula (3), ring A represents an aromatic ring which may have a substituent. ]

In general formula (3), the aromatic ring constituting ring A is a ring structure having aromaticity. The aromatic ring includes both a single ring and a condensed ring. The monocyclic ring is preferably a 5- or 6-membered ring, and preferably a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring. The fused ring is preferably 2 to 5 fused rings, and a naphthalene ring, anthracene ring, phenanthrene ring, or indole ring is preferable. Among these, the ring structure preferably does not contain a heteroatom as an atom constituting the ring structure. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, a halogen group, and the like.

Specific examples of the aromatic dicarboxylic acid imide include the following compounds.

The acidic group-containing aromatic compound has an aromatic ring and an acidic group directly bonded to the aromatic ring in the molecule. Examples of the acidic group include a carboxy group (-COOH), a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-OPO ₃ H ₂ ), a phosphonic acid group (-PO ₃ H ₂ ), and a phosphinic acid group (- PO ₂ H ₂ ). The number of acidic groups may be one or more. Moreover, when it has multiple acidic groups, it may have multiple types of acidic groups. The acidic group-containing aromatic compound is preferably a compound represented by the general formula (4) (namely, aromatic carboxylic acid, aromatic sulfonic acid, aromatic phosphonic acid).

〔一般式（４）において、環Ａは置換基を有していてもよい芳香環を表す。〕

[In general formula (4), ring A represents an aromatic ring which may have a substituent. ]

In general formula (4), the aromatic ring constituting ring A is a ring structure having aromaticity. The aromatic ring includes both a single ring and a condensed ring. The monocyclic ring is preferably a 5- or 6-membered ring, and preferably a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring. The fused ring is preferably 2 to 5 fused rings, and a naphthalene ring, anthracene ring, phenanthrene ring, or indole ring is preferable. Among these, the ring structure preferably does not contain a heteroatom as an atom constituting the ring structure. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, a halogen group, and the like.

Specific examples of the aromatic carboxylic acids include the following compounds.

Specific examples of the aromatic sulfonic acid include the following compounds.

Specific examples of the aromatic phosphonic acid include the following compounds.

The phenolic hydroxy group-containing aromatic compound has an aromatic ring and a hydroxy group directly bonded to the aromatic ring in the molecule. The number of hydroxy groups may be one or more. The phenolic hydroxy group-containing aromatic compound is preferably a compound represented by general formula (5).

〔一般式（５）において、環Ａは置換基を有していてもよい芳香環を表す。〕

[In general formula (5), ring A represents an aromatic ring which may have a substituent. ]

In general formula (5), the aromatic ring constituting ring A is a ring structure having aromaticity. The aromatic ring includes both a single ring and a condensed ring. The monocyclic ring is preferably a 5- or 6-membered ring, and preferably a benzene ring, a furan ring, a thiophene ring, or a pyrrole ring. The fused ring is preferably 2 to 5 fused rings, and a naphthalene ring, anthracene ring, phenanthrene ring, indole ring, coumarin ring, or xanthene ring is preferable. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, a halogen group, and the like.

Specific examples of the phenolic hydroxy group-containing aromatic compound include the following compounds.

(c) Tertiary amine compound The dispersant composition contains (c) a tertiary amine compound. The tertiary amine compound (c) has a tertiary amine structure in its molecule. When the dispersant composition contains the tertiary amine compound (c), it becomes possible to form a salt with the aromatic compound (b). (c) Only one type of tertiary amine compound may be blended, or two or more types may be used in combination.

The tertiary amine compound (c) is preferably a compound represented by general formula (6) or a compound represented by general formula (7), and more preferably a compound represented by general formula (7).

〔一般式（６）において、Ｒ⁶¹、Ｒ⁶²およびＲ⁶³は、それぞれ独立して、置換基を有してもよい炭素数１～１０の炭化水素基を示す。また、Ｒ⁶²およびＲ⁶³は互いに結合して環状構造を形成してよい。〕

[In general formula (6), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. Furthermore, R ⁶² and R ⁶³ may be combined with each other to form a cyclic structure. ]

The hydrocarbon group having 1 to 10 carbon atoms represented by R ⁶¹ , R ⁶² and R ⁶³ includes a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms. Examples include aryl groups having 7 to 10 carbon atoms, aralkyl groups having 7 to 10 carbon atoms, and alkylaryl groups having 7 to 10 carbon atoms.

Examples of the compound represented by the general formula (6) include aliphatic compounds such as trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, and N-ethyldiamylamine. Amines; aromatic amines such as N,N-dimethylaniline and N,N-diethylaniline; alicyclic amines such as N,N-dimethyl-cyclohexylamine and N,N-diethyl-cyclohexylamine; and the like.

〔一般式（７）において、Ｒ⁷¹は置換基を有してもよい炭素数２～６の２価の炭化水素基を示し、Ｒ⁷²およびＲ⁷³は、それぞれ独立して、水素原子または置換基を有してもよい炭素数１～１０の炭化水素基を示す。また、Ｒ⁷²およびＲ⁷³は互いに結合して環状構造を形成してよい。〕

[In general formula (7), R ⁷¹ represents a divalent hydrocarbon group having 2 to 6 carbon atoms which may have a substituent, and R ⁷² and R ⁷³ each independently represent a hydrogen atom or a substituent. Indicates a hydrocarbon group having 1 to 10 carbon atoms that may have a group. Furthermore, R ⁷² and R ⁷³ may be combined with each other to form a cyclic structure. ]

The divalent hydrocarbon group having 2 to 6 carbon atoms represented by R ⁷¹ includes an alkylene group having 2 to 6 carbon atoms. The substituents of the divalent hydrocarbon group having 2 to 6 carbon atoms represented by R ⁷¹ include a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, and a cyclic alkyl group having 6 carbon atoms. -10 aryl groups, C7-10 aralkyl groups, and C7-10 alkylaryl groups.

The hydrocarbon group having 1 to 10 carbon atoms represented by R ⁷² and R ⁷³ includes a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. , an aralkyl group having 7 to 10 carbon atoms, and an alkylaryl group having 7 to 10 carbon atoms.

As the compound represented by the general formula (7), a cyclic amidine compound represented by the general formula (8) is preferable.

〔一般式（８）において、Ｒ⁸⁰～Ｒ⁸⁹は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基、炭素数６～１０のアリール基を示す。ｎは、１～４の整数である。ｍは１～４の整数である。〕

[In general formula (8), R ⁸⁰ to R ⁸⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. n is an integer from 1 to 4. m is an integer from 1 to 4. ]

Specific examples of the compound represented by the general formula (8) include the following compounds.

The dispersant composition preferably contains a solvent. As the solvent, an organic solvent can be used, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxy Glycol monoalkyl ethers such as butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol Glycol dialkyl ethers such as dibutyl ether and dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether Acetate, glycol alkyl ether acetates such as triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate; ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1, Glycol diacetates such as 6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether, etc. Ethers of; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl Ketones such as pentanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol, etc. monohydric or polyhydric alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol Acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxy Chain or cyclic esters such as methyl propionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; 3-methoxypropionic acid, 3-ethoxypropionic acid, etc. Alkoxycarboxylic acids; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; and the like. The number of organic solvents contained in the dispersant composition may be one type or multiple types.

The dispersant composition can be prepared by mixing (a) a block copolymer, (b) an aromatic compound, (c) a tertiary amine compound, and, if necessary, a solvent. In addition, after mixing, (b) aromatic compound and (c) tertiary amine compound are considered to react and form an organic salt, so (b) aromatic compound and (c) tertiary amine compound are The mixture may be prepared by mixing the mixture with the compound and the block copolymer (a). The raw materials can be mixed using a mixing/dispersing machine such as a paint shaker, bead mill, ball mill, dissolver, or kneader. The mixing temperature when preparing the dispersant composition is preferably 50°C or higher, more preferably 55°C or higher, even more preferably 60°C or higher, and preferably 75°C or lower, more preferably 70°C or lower, even more preferably is below 65°C.

The dispersant composition has a molar ratio of the quaternary ammonium base in the block copolymer (a) to the aromatic compound (b) ((b)/quaternary ammonium base in (a)), It is preferably 0.5 or more, more preferably 0.8 or more, even more preferably 1.0 or more, and preferably 1.2 or less, more preferably 1.1 or less, still more preferably 1.05 or less.

The dispersant composition has a molar ratio of the quaternary ammonium base in the block copolymer (a) to the tertiary amine compound (c) ((c)/quaternary ammonium base in (a)). , is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and preferably 1.2 or less, more preferably 1.1 or less, still more preferably 1.05 or less. .

The dispersant composition has a molar ratio ((c)/((a ) is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.5 or more, and preferably 1.0 or less, more preferably 0.9 It is more preferably 0.8 or less.

In the dispersant composition, the molar ratio ((b)/(c)) between the aromatic compound (b) and the tertiary amine compound (c) is 0.8 or more, preferably 0.9. Above, it is more preferably 1.0 or more, 1.2 or less, preferably 1.1 or less, and more preferably 1.05 or less.

The amount of the solvent used is preferably 50 parts by mass or more, more preferably The amount is 100 parts by mass or more, more preferably 200 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 250 parts by mass or less.

The acid value of the solid content of the dispersant composition is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, and preferably 70 mgKOH/g or less, more preferably 60 mgKOH/g. g or less, more preferably 50 mgKOH/g or less. If the acid value is 5 mgKOH/g or more, the solubility in alkali is high and the rate of dissolution in alkali becomes faster, and if the acid value is 70 mgKOH/g or less, the viscosity of the coloring composition does not become too high and the resist composition Coating properties become better. Here, the solid content refers to components other than the solvent.

The amine value of the solid content of the dispersant composition is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 50 mgKOH/g or more, and preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g. g or less, more preferably 90 mgKOH/g or less. When the amine value is 10 mgKOH/g or more, the stability of the viscosity over time of the colored composition is further improved, and when the amine value is 150 mgKOH/g or less, the increase in the viscosity of the colored composition can be suppressed.

(Colored composition)
The colored composition of the present invention contains the dispersant composition, a coloring material having an aromatic ring, a dispersion medium, and a binder resin.

(Coloring material)
The type of the coloring material may be appropriately selected depending on the intended use as long as it has an aromatic ring in its structure, and examples thereof include pigments and dyes. The colored composition preferably contains a pigment as a coloring material from the viewpoint of light resistance and heat resistance. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment containing an organic compound as a main component is particularly preferred. Examples of the pigment include pigments of various colors such as red pigment, yellow pigment, orange pigment, blue pigment, green pigment, purple pigment, and black pigment. The structure of pigments is monoazo pigments, diazo pigments, azo pigments such as condensed diazo pigments, diketopyrrolopyrrole pigments, pyrromethene pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, and quinacridones. Examples include polycyclic pigments such as indigo pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments, and preferably azo pigments and diketo pigments. It is at least one selected from the group consisting of pyrrolopyrrole pigments, pyrromethene pigments, and dioxazine pigments. The number of pigments contained in the coloring composition may be only one, or multiple types may be included in order to adjust chromaticity and the like.

Specific examples of pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81:2, 81:3, 122, 123, 146, 149, 166, 168, Red pigments such as C.I. I. Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, Yellow pigments such as C.I. I. Pigment Orange 36, 38, 43, 71, 73, and other orange pigments; C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 22, 60, and other blue pigments; C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosphinyloxyaluminum phthalocyanine, diphenylphosphinyloxyaluminum phthalocyanine, polyhalogenated diphenoxy Green pigments such as phosphinyloxyaluminum phthalocyanine, polyhalogenated diphenylphosphinyloxyaluminum phthalocyanine; C. I. Examples include purple pigments such as Pigment Violet 23, 32, and 50. Among these pigments, C. I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81:2, 81:3, 122, 123, 146, 187, 200, 208, 210, 215, 254, 255, 264, 270, 272, 291; C. I. Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 150, 151, 154, 155, 166, 167, 168, 170, 180, 188, 194, 213; C. I. Pigment Orange 36, 38, 71, 73; C.I. I. Pigment Violet 23, 32, 50, etc. are preferred.

It is more preferable that the coloring material is a diaryl diketopyrrolopyrrole pigment having a structure represented by the following formula (13).

〔式（１３）中、Ａ¹およびＡ²は、それぞれ独立に、ハロゲン原子、メチル基、エチル基、ｔｅｒｔ－ブチル基、フェニル基、Ｎ，Ｎ－ジメチルアミノ基、トリフルオロメチル基、シアノ基を表し、ｊおよびｋはそれぞれ独立に０～５の整数を表す。ｊおよびｋがそれぞれ２以上の整数の場合、複数のＡ¹およびＡ²は、それぞれ同じであっても異なっていてもよい。〕

[In formula (13), A ¹ and A ² are each independently a halogen atom, methyl group, ethyl group, tert-butyl group, phenyl group, N,N-dimethylamino group, trifluoromethyl group, cyano group , and j and k each independently represent an integer from 0 to 5. When j and k are each integers of 2 or more, the plurality of A ¹ and A ² may be the same or different. ]

In the chemical formula (13), j and k are each independently an integer of 0 to 5. Among these, from the viewpoint of achieving high contrast and easily adjusting the red color suitable for color filters, it is preferable that j and k are each independently an integer of 0 to 3, and j and k are each independently 0 or 1. It is more preferable that there be.

Among the diketopyrrolopyrrole pigments, C.I. I. Pigment Red 254, 255, 264, 270, 272; C.I. I. Pigment Orange 71 and 73 are preferred. In addition, from the viewpoint of hue and tinting strength, C. I. Pigment Red 254, C. I. Pigment Red 255 is more preferred.

When forming a light shielding material such as a black matrix of a color filter using the colored composition of the present invention, a black pigment can be used. The black pigment may be used alone, or the red pigment, the green pigment, the blue pigment, etc. may be used in combination. Examples of the black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferred from the viewpoint of light shielding rate and image characteristics.

The number average particle diameter of the coloring material may be appropriately selected depending on its use, and is not particularly limited. The coloring composition preferably contains a coloring material having a number average particle diameter of 10 nm to 150 nm from the viewpoint of high transparency and high contrast.

The coloring material may contain a dye derivative as a dispersion aid. It is preferable that the dye derivative contains an acidic dye derivative having an acidic group in order to ionicly bond and adsorb the tertiary amino group and quaternary ammonium base in the resin-type dispersant. This dye derivative has an acidic functional group introduced into the dye skeleton. The pigment skeleton is preferably the same or similar to the coloring material constituting the coloring composition, or the same or similar to the compound serving as the raw material for the coloring material. The acidic group introduced into the dye skeleton is preferably a carboxy group, a phosphoric acid group, or a sulfonic acid group. Note that sulfonic acid groups are preferred for convenience of synthesis and strong acidity. Further, the acidic group may be directly bonded to the dye skeleton, or may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide, or urethane bond. The amount of the dye derivative to be used is not particularly limited, but is preferably from 4 parts by weight to 17 parts by weight, for example, based on 100 parts by weight of the colorant.

From the viewpoint of brightness, the upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 75% by mass, and 70% by mass in the total solid content of the coloring composition. It is more preferable. In addition, the lower limit of the content of the coloring material in the coloring composition is usually 10% by mass, preferably 30% by mass, and more preferably 50% by mass, based on the total solid content of the coloring composition. preferable. Here, the solid content refers to components other than the dispersion medium described below.

The content of the block copolymer (a) relative to the colorant in the coloring composition is preferably 5 parts by mass to 200 parts by mass, and 10 parts by mass to 100 parts by mass, based on 100 parts by mass of the colorant. The amount is preferably 10 parts by weight to 80 parts by weight, and more preferably 10 parts by weight to 80 parts by weight.

(dispersion medium)
The dispersion medium for the coloring composition may be appropriately selected as long as it disperses or dissolves the other components constituting the coloring composition, does not react with these components, and has appropriate volatility. It can be used as For example, conventionally known organic solvents can be used, and those exemplified as the solvent for the dispersant composition can be used. The organic solvent is preferably a glycol alkyl ether acetate or a monohydric or polyhydric alcohol from the viewpoint of dispersibility of the coloring material, solubility of the dispersant, coatability of the coloring composition, and the like. The coloring composition may contain only one type of solvent, or may contain multiple types.

When forming pixels of a color filter by photolithography, the boiling point of the dispersion medium is 100°C to 200°C (under a pressure of 1013.25 hPa; hereinafter, all boiling points are the same). preferable. Among the above-mentioned dispersion media, glycol alkyl ether acetates are preferred because they have a good balance in coating properties, surface tension, etc., and have relatively high solubility of constituent components in the coloring composition. Further, it is also preferable to use a dispersion medium having a boiling point of 150° C. or higher. By using a dispersion medium with a high boiling point in combination, it is possible to suppress the destruction of the mutual relationship between the colored compositions due to rapid drying of the colored compositions. Note that the dispersion medium having a boiling point of 150° C. or higher may be a glycol alkyl ether acetate.

The content of the dispersion medium in the coloring composition is not particularly limited and can be adjusted as appropriate. The upper limit of the content of the dispersion medium in the colored composition is usually 99% by mass. Further, the lower limit of the content of the dispersion medium in the coloring composition is usually 70% by mass, preferably 80% by mass, considering the viscosity suitable for application of the coloring composition. The dispersion medium can be used as a solvent for dissolving and removing precipitates formed from the colored composition.

(binder resin)
The colored composition of the present invention can contain a binder resin (excluding the block copolymer). As the binder resin, an alkali-soluble resin, a polymerizable compound (polymerizable resin, a monomer having one polymerizable unsaturated bond in the molecule, a monomer having two or more polymerizable unsaturated bonds in the molecule, an oligomer, etc.) , thermosetting resin, thermoplastic resin, etc. These can be used alone or in combination of two or more. Among these, preferred are alkali-soluble resins and/or polymerizable compounds.

The content of the binder resin in the coloring composition is the total amount of binder resin used, and is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass based on the total solid content of the coloring composition. The content is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less.

(alkali availability resin)
The alkali-soluble resin may act as a binder for the coloring material and be soluble in a developer used in the development process when producing a color filter, preferably an alkaline developer. For example, although not particularly limited, a resin having an acidic group such as a carboxy group or a phenolic hydroxy group is preferable.

The alkali-soluble resin may be, for example, a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, in which at least a portion of the epoxy groups in the copolymer are unsaturated. A resin obtained by adding a basic acid, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction; A linear resin containing a carboxyl group in the main chain; Examples include resins in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of a group-containing resin; (meth)acrylic resins; epoxy (meth)acrylate resins having a carboxyl group; these may be used singly or in combination. A mixture of two or more species can be used.

The alkali-soluble resin is a random copolymer containing a structural unit derived from a carboxyl group-containing vinyl monomer, a structural unit derived from (meth)acrylate, and styrene, or an epoxy resin in which a (meth)acrylic group is introduced. A random copolymer containing a structural unit derived from a synthetic resin or a carboxyl group-containing vinyl monomer and a structural unit derived from a (meth)acrylate is preferred. As the carboxy group-containing vinyl monomer, (meth)acrylic acid is preferable. The (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and cyclohexyl (meth)acrylate. , isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, 2-hydroxylethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycerol mono( Examples include meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

The alkali-soluble resin preferably has a total content of structural units derived from carboxyl group-containing vinyl monomers and structural units derived from (meth)acrylates of 50% by mass or more, more preferably 60% by mass or more, and even more preferably is 70% by mass or more. Further, the alkali-soluble resin preferably has a structure derived from a carboxyl group-containing vinyl monomer of 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 90% by mass. It is preferably at most 70% by mass, more preferably at most 70% by mass.

Among the alkali-soluble resins, a random copolymer of a carboxyl group-containing vinyl monomer and (meth)acrylate is preferred. Specific examples of such copolymers include random copolymers of (meth)acrylic acid and butyl (meth)acrylate, random copolymers of (meth)acrylic acid and benzyl (meth)acrylate, and random copolymers of (meth)acrylic acid and benzyl (meth)acrylate. ) A random copolymer of acrylic acid, butyl (meth)acrylate, and benzyl (meth)acrylate, and the like. From the viewpoint of affinity between the alkali-soluble resin and the colorant, the alkali-soluble resin is particularly preferably a random copolymer of (meth)acrylic acid and benzyl (meth)acrylate. In the copolymer of a carboxyl group-containing vinyl monomer and (meth)acrylate, the content of (meth)acrylic acid is usually 5% to 90% by mass, and 10% to 70% by mass based on the total monomer components. It is preferably 20% by mass to 70% by mass. The polymerization method for these random copolymers is not particularly limited, but living radical polymerization is preferred from the viewpoint of alkali solubility.

The alkali-soluble resin may have a radically polymerizable carbon-carbon double bond in its side chain. By having a double bond in the side chain, the photocurability of the colored composition according to the present invention increases, so that resolution and adhesion can be further improved. Examples of methods for introducing a radically polymerizable carbon-carbon double bond into the side chain include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o-(or m-, or p- ) A method of reacting a compound such as vinylbenzyl glycidyl ether with the acidic group of the binder resin may be mentioned.

The Mw of the alkali-soluble resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 20,000. If the Mw of the alkali-soluble resin is 3,000 or more, the heat resistance, film strength, etc. of the colored layer formed from the colored composition will be good, and if the Mw is 100,000 or less, the alkali development of this coating film will be good. The properties will be even better.

The acid value of the alkali-soluble resin is preferably 20 mgKOH/g to 170 mgKOH/g, more preferably 50 mgKOH/g to 150 mgKOH/g, and even more preferably 90 mgKOH/g to 150 mgKOH/g. When the acid value of the alkali-soluble resin is 20 mgKOH/g or more, the alkali developability when the colored composition is used as a colored layer becomes even better, and when it is 170 mgKOH/g or less, the heat resistance becomes better.

The coloring composition may contain only one type of alkali-soluble resin, or may contain multiple types. In the coloring composition, the content of the alkali-soluble resin is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass, and 20 parts by mass, based on 100 parts by mass of the colorant. More preferably, the amount is from parts by weight to 80 parts by weight.

(Polymerizable compound)
The polymerizable resin as the polymerizable compound (for example, a (meth) Acrylic compounds, resins with crosslinking groups such as cinnamic acid introduced), compounds having one polymerizable unsaturated bond in the molecule (e.g., monofunctional (meth)acrylic monomers (alkyl (meth)acrylates, aralkyl (meth) acrylate, etc.)), compounds having two or more polymerizable unsaturated bonds in the molecule (e.g., polyfunctional (meth)acrylic monomers (di(meth)acrylate of dihydric alcohol, poly(meth)acrylate of trivalent or higher polyhydric alcohol), (meth)acrylate etc.)), etc. Examples of the polymerizable unsaturated bond include a carbon-carbon double bond and a carbon-carbon triple bond. These can be used alone or in combination of two or more. Among these, compounds having two or more polymerizable unsaturated bonds in the molecule are preferred.

Examples of monomers having two or more polymerizable unsaturated bonds in the molecule as the polymerizable compound include bisphenol A di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,3-butylene glycol di(meth)acrylate. (meth)acrylate, diethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta Examples include (meth)acrylate.

The content of the polymerizable compound in the coloring composition is preferably 10 parts by mass to 1,000 parts by mass, particularly preferably 20 parts by mass to 500 parts by mass, based on 100 parts by mass of the colorant. If the content of the polymerizable compound is within the above range, sufficient curability will be obtained and the alkali developability will also be good. It is also preferable to use an alkali-soluble resin and a polymerizable compound together as the binder resin.

(thermosetting resin, thermoplastic resin)
Examples of the thermosetting resin and thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyurethane resin, phenolic resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin etc.

(Photopolymerization initiator)
The colored composition preferably contains a photopolymerization initiator. Thereby, radiation sensitivity can be imparted to the colored composition. The photopolymerization initiator is a compound that generates active species capable of initiating polymerization of the crosslinking agent upon exposure to radiation such as visible light, ultraviolet rays, far infrared rays, electron beams, and X-rays.

Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, and α-diketones. Examples include polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, aminoketone compounds, and the like. The photopolymerization initiators can be used alone or in combination of two or more.

In the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 parts by mass to 120 parts by mass, particularly preferably 1 part by mass to 100 parts by mass, based on 100 parts by mass of the polymerizable compound. In this case, if the content of the photopolymerization initiator is too small, curing may be insufficient due to exposure, whereas if it is too large, the formed colored layer tends to easily fall off from the substrate during development.

(Other combination agents)
In addition to the above-mentioned compounding agents, other compounding agents can be added to the coloring composition as long as they do not impair the preferred physical properties of the present invention. Other additives include sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, and organic carboxylic acid compounds. Acid anhydrides, pH adjusters, antioxidants other than the above phenolic antioxidants, ultraviolet absorbers, light stabilizers, preservatives, fungicides, anti-agglomeration agents, adhesion improvers, development improvers, storage stability Agents, etc. can be mentioned.

Sensitizing dyes include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3 , 4-diaminobenzophenone, 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-( p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzothiazole, -diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)1,3,4-thiadiazole, ( p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc. can be mentioned.

Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, and β-naphthol.

Examples of nonionic surfactants include fluorine surfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluoropropyl) Fluorooctylhexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol Di(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1, 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc.), silicone surfactants, polyoxyethylene surfactants agents (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin) fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, etc.) Can be mentioned.

Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, aliphatic Alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer surfactants agents, etc.
Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.
Examples of amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, amino acids, and the like.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerin, and the like.

Examples of organic carboxylic acid compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid; Aliphatic tricarboxylic acids such as tricarballylic acid and aconitic acid; benzoic acid Aromatic carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as , phthalic acid, trimesic acid, pilopete acid, and merophanic acid; phenyl groups such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, phenylsuccinic acid, and cinnamylindenacetic acid. Examples include aromatic carboxylic acids to which a carboxyl group is bonded via a carbon bond. By containing an organic carboxylic acid compound, alkali developability and scumming can be improved.

Examples of organic carboxylic anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2- Examples include cyclohexenedicarboxylic acid, n-octadecylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, and the like. By containing an organic carboxylic acid anhydride, alkali developability and scumming can be improved.

<Method for producing colored composition>
The colored composition can be prepared by mixing a dispersant composition, a coloring material, a dispersion medium, a binder resin, and if necessary a photopolymerization initiator, other additives, and the like. The colored composition includes (a) a block copolymer, (b) an aromatic compound, (c) a tertiary amine compound, a coloring material, a dispersion medium, a binder resin, and other components as necessary. It may be prepared by For mixing, for example, a mixing and dispersing machine such as a paint shaker, bead mill, ball mill, dissolver, or kneader can be used. Preferably, the colored composition is filtered after mixing. Examples of other additives include pH adjusters, antioxidants, ultraviolet absorbers, light stabilizers, preservatives, antifungal agents, surfactants, and anti-agglomeration agents.

Since the coloring composition has excellent dispersibility, it can be suitably used for color filters.

<Color filter>
The color filter of the present invention includes a colored layer formed using the colored composition. Examples of methods for manufacturing color filters include the following method. First, thermoplastic resin sheets such as polyester resins, polyolefin resins, polycarbonate resins, and polymethyl methacrylate resins, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, various glasses, etc. After applying the colored composition of the present invention in which, for example, a red pigment is dispersed, onto a transparent substrate, prebaking is performed to evaporate the solvent (dispersion medium) to form a coating film. Next, this coating film is exposed to light through a photomask, and then developed using an alkaline developer (such as an organic solvent or an aqueous solution containing a surfactant and an alkaline compound) to dissolve and remove the unexposed areas of the coating film. do. Thereafter, by post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed. Next, each coloring composition of green or blue is applied, pre-baked, exposed, developed and post-baked in the same manner as above to form a green pixel array and a blue pixel array on the same substrate. Form on top one after another. As a result, a color filter is obtained in which pixel arrays of the three primary colors of red, green, and blue are arranged on the substrate. However, in the present invention, the order in which pixels of each color are formed is not limited to the above.

When applying the colored composition to the substrate, an appropriate application method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, etc. can be adopted. In particular, it is preferable to employ a spin coating method or a slit die coating method.
After forming a protective film as necessary on the pixel pattern thus obtained, a transparent conductive film (ITO or the like) is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter. Further, a black matrix may be provided on the transparent substrate used to form the pixel array of the three primary colors of red, green, and blue.

The color filter of the present invention has high dimensional accuracy and can be suitably used for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples in any way, and can be implemented with appropriate modifications within the scope of the gist. The polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), amine value and acid value of the dispersant and binder resin, and the viscosity of the colored composition were evaluated according to the following methods.

The meanings of the abbreviations are as follows.
BTEE: Ethyl-2-methyl-2-n-butyltellanyl-propionate DBDT: Dibutyl ditelluride AIBN: 2,2'-azobis(isobutyronitrile)
BMA: Butyl methacrylate CL5MA: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Co., Ltd., Plaxel (registered trademark) FM5)
DMAEMA: dimethylaminoethyl methacrylate BzCl: benzyl chloride MAA: methacrylic acid PI: phthalimide 2-NA: 2-naphthoic acid 4-MU: 4-methylumbelliferone DBU: diazabicycloundecene TEA: triethylamine PMA: propylene glycol monomethyl Ether acetate MP: 1-methoxy-2-propanol

(Polymerization rate)
¹ H-NMR was measured using a nuclear magnetic resonance (NMR) measuring device (manufactured by Bruker, model: AVANCE 500 (frequency 500 MHz)) (solvent: deuterated chloroform, internal standard: tetramethylsilane). Regarding the obtained NMR spectrum, the integral ratio of the peaks of the vinyl group derived from the monomer and the ester side chain derived from the polymer was determined, and the polymerization rate of the monomer was calculated.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It was determined by gel permeation chromatography (GPC) using a high performance liquid chromatograph (manufactured by Tosoh, model: HLC8320). The column is one SHODEX KF-603 (Φ6.0mm x 150mm) (manufactured by SHODEX), mobile phase is 30mmol/L lithium bromide-30mmol/L acetic acid-N-methylpyrrolidone, and the detector is a differential refractive index detector. It was used. The measurement conditions were a column temperature of 40° C., a sample concentration of 20 mg/mL, a sample injection amount of 10 μL, and a flow rate of 0.2 mL/min. A calibration curve was created using polystyrene (molecular weight: 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) as a standard substance, and the weight average molecular weight ( Mw) and number average molecular weight (Mn) were measured. Molecular weight distribution (PDI=Mw/Mn) was calculated from these measured values.

(amine value)
The amine value is expressed by the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of solid content. The measurement sample was dissolved in tetrahydrofuran, and the resulting solution was subjected to neutralization titration with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potentiometric titration device (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The amine value (B) was calculated using the following formula, using the inflection point of the titration pH curve as the titration end point.
B=56.11×Vs×0.1×f/w
B: Amine value (mgKOH/g)
Vs: Amount of 0.1 mol/L hydrochloric acid/2-propanol solution required for titration (mL)
f: Titer of 0.1 mol/L hydrochloric acid/2-propanol solution w: Mass of measurement sample (g) (solid content conversion)

(Acid value)
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. The measurement sample was dissolved in tetrahydrofuran, several drops of phenolphthalein ethanol solution was added as an indicator, and neutralization titration was performed with 0.1 mol/L potassium hydroxide/ethanol solution. The acid value (A) was calculated using the following formula.
A=56.11×Vs×0.1×f/w
A: Acid value (mgKOH/g)
Vs: Amount of 0.1 mol/L potassium hydroxide/ethanol solution used for titration (mL)
f: Potency of 0.1 mol/L potassium hydroxide/ethanol solution w: Mass of measurement sample (g) (solid content conversion)

(viscosity)
Viscosity was measured using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.) using a cone rotor (1°34'×R24) at 25° C. and a rotor rotation speed of 60 rpm.
After the colored composition was prepared, it was stored at 25° C. for 2 hours, and then its viscosity was measured. Those with a viscosity of less than 10 mPa·s were evaluated as “A”, and those with a viscosity of 10 mPa·s or more were evaluated as “B”.

<Production of block copolymer>
A flask equipped with an argon gas inlet tube and a stirrer was charged with 50.4 g of BMA, 199.5 g of CL5MA, 16.1 g of MAA, 0.82 g of AIBN, and 80.5 g of PMA, and after replacing with argon, BTEE 14.99 g, DBDT 9 .23g was added and reacted at 60°C for 5 hours to polymerize block A. The polymerization rate was 98%.

A mixed solution of 83.9 g of DMAEMA and 28.0 g of PMA, which had been substituted with argon in advance, was added to the reaction solution, and the mixture was reacted at 60° C. for 10 hours to polymerize the B block. The polymerization rate was 100%.

After the reaction was completed, the reaction solution was diluted by adding 125 g of methanol which had been substituted with argon in advance, and 13.5 g of BzCl was added to the diluted solution, and the mixture was reacted at 60° C. for 10 hours to quaternize it.

After the reaction was completed, the reaction solution was poured into stirring n-heptane. A block copolymer was obtained by suction filtration and drying of the precipitated polymer. The obtained block copolymer had an Mw of 13968, a PDI of 1.56, an acid value of 33 mgKOH/g, an amine value of 64 mgKOH/g, and an A block content of 71.5% by mass in the copolymer. The content of the B block is 28.5% by mass, the content of structural units derived from vinyl monomers having acidic groups in the copolymer is 4.4% by mass, and the content is expressed by general formula (1) in the copolymer. The total content of the structural units represented by the formula (2) and the structural units represented by the general formula (2) was 26.8% by mass. The content of each structural unit in the copolymer was calculated from the charging ratio of the vinyl monomer used in the polymerization reaction, the polymerization rate of the vinyl monomer, and the reaction rate of the quaternizing agent used in the quaternization reaction.

<Preparation of dispersant composition>
(Dispersant composition No.A)
44.3 g of block copolymer, 1.94 g of PI, 2.07 g of DBU, 106 g of PMA, and 6.85 g of MP were added to a flask equipped with a stirrer, and heated and mixed at 60°C for 20 hours to form a dispersant composition. Prepared.

(Dispersant composition No.B to D)
By changing the formulation of each component as shown in Table 1, dispersant composition No. Dispersant composition No. B, C, and D were obtained.

<Synthesis of alkali-soluble resin A>
A flask equipped with an argon gas introduction tube and a stirrer was charged with methacrylic acid (MAA) (40.0 g), benzyl methacrylate (BzMA) (160.0 g), and propylene glycol monomethyl ether acetate (PMA) (580.0 g). After replacing the mixture with argon, 2,2'-azobis(isobutyronitrile) (AIBN) (4.0 g), n-dodecanethiol (6.0 g), and PMA (20.0 g) were added, and the temperature was raised to 90°C. MAA (80.0 g), BzMA (320.0 g), AIBN (8.0 g), n-dodecanethiol (12.0 g), and PMA (50.0 g) were added to the solution while keeping the solution at 90°C. The mixture was added dropwise over 1.5 hours. 60 minutes after the dropwise addition was completed, the temperature was raised to 110°C, AIBN (0.8 g) and PMA (10.0 g) were added and reacted for 1 hour, and further AIBN (0.8 g) and PMA ( 10.0 g) was added and reacted for 1 hour, and further AIBN (0.8 g) and PMA (10.0 g) were added and reacted for 1 hour.

The obtained reaction solution was cooled to room temperature, and PMA (240.0 g) was added to obtain a solution of binder resin A with a nonvolatile content of 39.5%. Alkali-soluble resin A had a weight average molecular weight (Mw) of 9,150, a molecular weight distribution (PDI) of 1.92, and an acid value of 128 mgKOH/g.

<Preparation of colored composition>
(Coloring composition No. 1)
The blending composition was adjusted to 8 parts by mass of pigment, 5 parts by mass of dispersant composition, 5 parts by mass of alkali-soluble resin, and 82 parts by mass of PMA, 555 parts by mass of 0.3 mm zirconia beads were added, and a bead mill (product name: DISPERMAT) was prepared. CA, VMA-GETZMANN GmbH) for 3 hours to fully disperse the mixture. After the dispersion was completed, the beads were filtered to obtain a colored composition. The dispersant composition includes Dispersant Composition No. A was used as the alkali-soluble resin, and alkali-soluble resin A was used as the alkali-soluble resin, and C. I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) was used. The viscosity of the obtained colored composition was evaluated. The results are shown in Table 2.

(Coloring composition No. 2 to 5)
Coloring composition No. 1 was used except that the dispersant was changed to one shown in Table 2. Coloring composition No. 1 was prepared in the same manner as in the preparation method of No. 1. 2 to 5 were prepared. Coloring composition No. In No. 5, the block copolymer obtained above was used as a dispersant.

As a dispersant, dispersant composition No. Coloring composition No. using A to D. Samples 1 to 4 had high pigment dispersibility and low viscosity.

The block copolymer of the present invention can be used as a dispersant for a colorant in a coloring composition. The colored composition can be suitably used for color filters. The color filter has high dimensional accuracy and can be suitably used for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Claims (13)

A dispersant composition used in a coloring composition containing a colorant having an aromatic ring as a colorant,
(a) An A block containing a structural unit derived from a vinyl monomer having an acidic group, and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). and the content of the structural unit derived from the vinyl monomer having an amino group in the A block is 2% by mass or less, and the content of the structural unit represented by the general formula (1) is 100% by mass of the B block. A block copolymer in which the content of the structural unit represented by the general formula (2) is 15% by mass or more in 100% by mass of B block, which is 10% by mass or more in mass%,
(b) at least one aromatic compound selected from the group consisting of aromatic dicarboxylic acid imide, acidic group-containing aromatic compound, and phenolic hydroxy group-containing aromatic compound, and
(c) mixed with a tertiary amine compound;
A dispersant composition characterized in that the molar ratio ((b)/(c)) of the aromatic compound (b) to the tertiary amine compound (c) is 0.8 to 1.2.

[In formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion. ]

[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ] The dispersant composition according to claim 1, wherein the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is 80% by mass or more. thing. The molar ratio of the quaternary ammonium base in the block copolymer (a) to the aromatic compound (b) ((b)/quaternary ammonium base in (a)) is 0.5 to 1.2. The dispersant composition according to claim 1 or 2 . The molar ratio of the quaternary ammonium base in the block copolymer (a) to the tertiary amine compound (c) ((c)/quaternary ammonium base in (a)) is 0.5 to 1. The dispersant composition according to any one of claims 1 to 3, which is No. 2. The dispersant composition according to any one of claims 1 to 4 , wherein the content of structural units derived from a vinyl monomer having an acidic group in the block copolymer (a) is 1% by mass to 20% by mass. thing. A claim in which the total content of the structural units represented by the general formula (1) and the structural units represented by the general formula (2) in the block copolymer (a) is 5% by mass to 50% by mass. The dispersant composition according to any one of Items 1 to 5 . The dispersant according to any one of claims 1 to 6, wherein the tertiary amine compound (c) is a compound represented by general formula (6) and/or a compound represented by general formula (7). Composition.

[In general formula (6), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. Furthermore, R ⁶² and R ⁶³ may be combined with each other to form a cyclic structure. ]

[In general formula (7), R ⁷¹ represents a divalent hydrocarbon group having 2 to 6 carbon atoms which may have a substituent, and R ⁷² and R ⁷³ each independently represent a hydrogen atom or a substituent. Indicates a hydrocarbon group having 1 to 10 carbon atoms that may have a group. Furthermore, R ⁷² and R ⁷³ may be combined with each other to form a cyclic structure. ] Containing the dispersant composition according to any one of claims 1 to 7 , a colorant, a dispersion medium and a binder resin,
A colored composition, wherein the coloring material has an aromatic ring. (a) An A block containing a structural unit derived from a vinyl monomer having an acidic group, and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). and the content of the structural unit derived from the vinyl monomer having an amino group in the A block is 2% by mass or less, and the content of the structural unit represented by the general formula (1) is 100% by mass of the B block. A block copolymer in which the content of the structural unit represented by the general formula (2) is 15% by mass or more in 100% by mass of the B block, (b) aromatic At least one aromatic compound selected from the group consisting of a dicarboxylic acid imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound, (c) a tertiary amine compound, a colorant having an aromatic ring, and a dispersion. It is made by mixing a medium and a binder resin,
A colored composition characterized in that the molar ratio ((b)/(c)) between the aromatic compound (b) and the tertiary amine compound (c) is 0.8 to 1.2.

[In formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion. ]

[In formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ] The colored composition according to claim 9, wherein the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is 80% by mass or more. . According to any one of claims 8 to 10 , the coloring material is at least one selected from the group consisting of an azo pigment, a diketopyrrolopyrrole pigment, a pyrromethene pigment, and a dioxazine pigment. coloring composition. The colored composition according to any one of claims 8 to 11 , which is used for color filters. A color filter comprising a colored layer formed using the colored composition according to claim 12 .